On the inclusion of one double within CIS and TDDFT

Abstract

We present an improved approach for generating a set of optimized frontier orbitals (HOMO and LUMO) that minimizes the energy of one double configuration. We further benchmark the effect of including such a double within a rigorous configuration interaction singles or a parameterized semi-empirical time-dependent density functional theory Hamiltonian for a set of test cases. Although we cannot quite achieve quantitative accuracy, the algorithm is quite robust and routinely delivers an enormous qualitative improvement to standard single-reference electronic structure calculations.